Na₃FeH₇ and Na₃CoH₆: Hydrogen-Rich First-Row Transition Metal Hydrides from High Pressure Synthesis

The formation of ternary hydrogen-rich hydrides involving the first-row transition metals TM = Fe and Co in high oxidation states is demonstrated from in situ synchrotron diffraction studies of reaction mixtures NaH-TM-H₂ at p ≈ 10 GPa. Na₃FeH₇ and Na₃CoH₆ feature pentagonal bipyramidal FeH₇^3- and octahedral CoH₆^3- 18-electron complexes, respectively. At high pressure, high temperature (300 < T ≤ 470 °C) conditions, metal atoms are arranged as in the face-centered cubic Heusler structure, and ab initio molecular dynamics simulations suggest that the complexes undergo reorientational dynamics. Upon cooling, subtle changes in the diffraction patterns evidence reversible and rapid phase transitions associated with ordering of the complexes. During decompression, Na₃FeH₇ and Na₃CoH₆ transform to tetragonal and orthorhombic low pressure forms, respectively, which can be retained at ambient pressure. The discovery of Na₃FeH₇ and Na₃CoH₆ establishes a consecutive series of homoleptic hydrogen-rich complexes for first-row transition metals from Cr to Ni.